JPH05194784A - Photopolymerizable organic composition - Google Patents

Abstract

PURPOSE: To photo-cure a composition obtained by photopolymerizing photopolymerizable organic materials such as epoxy resins to a greater depth and thickness.

CONSTITUTION: Photopolymerizable organic resin compositions are comprised of (A) photopolymerizable organic materials and (B) photoinitiators comprising aryl ketone-containing diaryliodonium salts having the formula; R¹-I⁺-RX^- (wherein R is a 6-13C monovalent aromatic hydrocarbon group or halo substituted monovalent aromatic hydrocarbon group and R¹ is a monovalent aryl ketone group which is attached to iodine by a nuclear carbon atom to form a carbon-iodine bond, and X^- is a counter ion). The photoinitiators (B) having monovalent aryl ketone groups can effect deep section cure of (A) photopolymerizable organic materials and cure the materials to greater thickness, as compared to the diaryliodonium salts of the prior arts.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to arylketone-containing iodonium salts, a process for their synthesis and their use as photoinitiators in photopolymerizable organic materials.

[0002]

Prior to the present invention, diaryl iodonium salts, such as diphenyl iodonium hexafluoroarsenate, were used for the cationic polymerization of epoxy resins as disclosed in Smith, U.S. Pat. No. 4,378,277. It was used as an initiator.

[0003]

While the above-mentioned diaryliodonium salts have been effective in converting epoxy resins to tack free states in a relatively short time, cured films are often necessary to activate diaryliodonium salts. It is often difficult to obtain a cured epoxy resin product with a satisfactory thickness, as it acts as a barrier to strong UV radiation. Hardened coating with improved thickness is Smith
This has been accomplished by using certain sulfonium salts, as shown in U.S. Pat. No. 4,173,476. It is therefore desirable to use diaryliodonium salts in special applications to achieve deeper cure in UV-polymerizable organic materials.

[0004]

The present invention, there is provided a means for solving] The formula: R ¹ -I ⁺ -R X ^{- i.e., [RR 1 I] + X} - (1) ( wherein, R C _(6-13) monovalent An aromatic hydrocarbon group or a halo-substituted monovalent aromatic hydrocarbon group, R ¹ is a monovalent arylketone group linked to iodine by a nuclear carbon atom, and X ⁻ is a counterion). The arylketone-containing diaryliodonium salts are based on the new finding that they can be used for the preparation of deep photopolymerizable organic materials with a wide range of photopolymerizable organic materials such as epoxy resins. The arylketone-containing diaryliodonium salt of formula (1) can be prepared by simple metathesis between a diaryliodonium tosylate precursor and a suitable counterion source such as a hexafluorometal salt or a metalloid salt. The diaryl iodonium tosylate salt precursor can be prepared by directly condensing an aryl iodosotosylate and an aromatic ketone according to the following formula. That is,

[0005]

[Chemical 5] (Wherein Tos ⁻ is tosylate and R and R ¹ are as defined above.) The synthesis of diaryl iodonium salts involving the direct condensation of aryl iodosotosylate is described by Koser, Wetach and Smith in J.
individual of Organic Chemist
ry, 45 , 1944 (1980).
As mentioned above, the conversion of arylketone-containing aryliodonium tosylate to arylketone-containing diaryliodonium salt having the formula (1) can be accomplished by simple metathesis as shown by the following formula. That is,

[0006]

Embedded image [RR ¹ I] ⁺ Tos ⁻ + MX → Formula (1) + MTos ⁻ (In the formula, M is a metal or a metalloid.)

[0007]

EXAMPLES According to the present invention, (A) a photopolymerizable organic substance;
And (B) an effective amount of the aryl ketone-containing iodonium photoinitiator of the formula (1);

Groups within the scope of R in formula (1) include C _(6-13) monovalent aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, anthryl groups and up to 1 to 4 groups. Monovalent groups such as C _(1-8) alkoxy, C
_(1-8) C _(6-13) monovalent aromatic hydrocarbon group benzoyl substituted with a group such as alkyl, nitro, chloro and hydroxy,
An arylacyl group such as phenylacyl; an aromatic heterocyclic group such as pyridyl, furfuryl and the like.

Groups included within R ¹ of formula (1) are, for example:

[0010]

[Chemical 7]

[0011]

[Chemical 8]

[0012]

[Chemical 9]

[0013]

[Chemical 10]

[0014] X in formula (1)^-Yin Yi included in
Example of ON is BF_Four ^-, PF₆ ^-, AsF₆ ^-, SbF₆
^-, ClO_Four ^-, CF₃SO₃ ^-, FSO₃ ^-, CF₃
CO₂ ^-, AlCl_Four ^-, BCl_Four ^-, Br^-, C
l^-, HSO_Four ^-, CH₃CO₂ ^-, NO ₃ ^-, Etc.
It

Examples of compounds included within the scope of arylketone-containing iodonium salts of formula (1) are as follows:

[0016]

[Chemical 11]

[0017]

[Chemical formula 12]

[0018]

[Chemical 13]

[0019]

[Chemical 14]

[0020]

[Chemical 15]

[0021]

[Chemical 16]

[0022]

[Chemical 17]

[0023]

[Chemical 18]

The term "epoxy resin" as used in the description of the photopolymerizable compositions of the present invention refers to any monomeric, dimeric or oligomeric form containing one or more epoxy functional groups. It includes polymeric epoxy materials. For example, the epoxy resin resulting from the reaction of bisphenol-A (4,4'-isopropylidenediphenol) with epichlorohydrin or the epoxy resin obtained by the reaction of low molecular weight phenol formaldehyde resin (novolak resin) with epichlorohydrin may be used alone or in reaction. It can be used in combination with an epoxy-containing compound as a functional diluent. Phenylglycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide,
1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide,
Diluents such as allyl glycidyl ether may be added as viscosity modifiers.

Further, the range of these compounds may be extended to include polymeric materials containing terminal or pendant epoxy groups. An example of these compounds is a vinyl copolymer containing glycidyl acrylate or methacrylate as one of the comonomers. Another group of epoxy-containing polymers that can be cured with the above catalysts are epoxy siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and methods for making them are especially described by E.I. P. Pludemann and G.W. Fa
by Nger. Am. Chem. Soc. , 8
0, is described in 632-5 (1959). As shown therein, epoxy resins can be further modified in various standard ways, such as by reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc. (eg US Pat. No. 2,935,488). ,
No. 3,235,620, No. 3,369,055, No. 3,379,653, No. 3,398,211, No. 3,403,199, No. 3,563,840, No. 3 , 567,797, 3,677,995). Another co-reactant that may be used with the epoxy resin is Interscience Publishers,
Published in 1967, Encyclopedia of P
polymer Science and Techno
and hydroxy-terminated softeners such as the hydroxy-terminated polyesters shown in Loggy, Volume 6, pages 209-271, especially 238.

Photopolymerizable organic materials that can be used in the practice of the present invention include thermosetting organic condensation resins for formaldehyde, such as urea resins and phenol-formaldehyde resins. In addition, melamine thiourea resin, melamine,
Alternatively, a combination of urea aldehyde resins, cresol-formaldehyde resins and polyesters, alkyds and other carboxy, hydroxy, amino and mercapto containing resins such as polysulfides may be used.

Some examples of vinyl organic prepolymers that can be used to make the polymerizable compositions of the present invention are CH ₂ ═CH—O.
_{- (CH 2 -CH 2 O)} n '-CH = CH 2 ( in the formula,
n'is a positive integer with a value of up to about 1000 or more); polyfunctional vinyl ethers such as 1,2,
3-propanetrivinylether, trimethylpropanetrivinylether; Formula:

[0028]

[Chemical 19]

A prepolymer having; and 200 at 25 ° C.
Low molecular weight polybutadiene having a viscosity of ˜10,000 centipoise. The products obtained by curing such compositions can be used as printing inks and in other applications typical of thermosetting resins. Yet another type of photopolymerizable organic material that can be used to make the polymerizable compositions of the present invention are cyclic ethers that can be converted into thermoplastics. Included in such cyclic ethers are oxetanes such as 3,3-bis-chloromethyl oxetane, alkoxy oxetanes such as those shown in Schroeter, U.S. Pat. No. 3,673,216. Oxolanes such as tetrahydrofuran, oxepanes, oxygen-containing spiro compounds, trioxane, dioxolane and the like.

In addition to cyclic ethers, β-lactones,
Cyclic esters such as propiolactone;
Cyclic amines and formulas such as 1,3,3-trimethylazetidine:

[0031]

[Chemical 20]

Cyclic organosilicon compounds included in the formula (wherein R "is a monovalent organic group which may be the same or different, such as methyl or phenyl, and m is an integer of 3 to 8). Examples of cyclic organosilicon compounds that can be included in such photopolymerizable organic materials are hexamethyltrisiloxane, octamethyltetrasiloxane, etc. The products produced in accordance with the present invention are high molecular weight oils and gums. ..

In the practice of the present invention, the aryl ketone-containing iodonium salt of formula (1) can be prepared by reacting an aryl iodosotosylate with an aromatic ketone at a temperature in the range of about 25 to 125 ° C. In special cases, the reaction can be carried out in the molten state or suitable organic solvents can be used to accelerate the reaction. Suitable aromatic ketones which can be used are, for example, benzophenone, acetophenone, propiophenone, 4
-Benzoylbenzoic acid, 4-benzoylbiphenyl, 4
-Bromobenzophenone, 2-chlorobenzophenone,
3-nitrobenzophenone, 4,4'-dimethoxybenzophenone, 4-hydroxybenzophenone, 9-fluorenone, thioxanthone, anthriquinone, naphthoquinone, acridone, benzyl 1-benzoylnaphthalene, 1-tetralone, xanthone, 4-chlorothioxanthone, 4-acetyl Examples include biphenyl and α-bromoacetophenone.

In special cases, inert organic solvents can be used to accelerate the reaction. Examples of such inert organic solvents that can be used include chloroform, methylene chloride, acetic acid, nitromethane, acetonitrile, carbon tetrachloride and the like. Aromatic ketones containing aryl iodonium tosylate defined the X ^- Metal salts of a counterion giving suitable anions encompassed or metalloid salt or hydrogen substituted sources formula by metathesis reaction such described above with reference to (1)
Can be converted to an aromatic iodonium salt containing an aromatic ketone. Suitable metal or metalloid salts that can be used in the metathesis reaction are shown, for example, in Crivello, US Pat. No. 4,173,551. Examples of these metal salts or metalloid salts are Sb, Fe, Sn,
Bi, Al, Ga, In, Ti, Zr, Sc, V, C
transition metals such as r, Mn and Co, lanthanides such as Ce, Pr, Nd, actinides such as T
rare earth elements such as h, Pa, U, Np and B, P,
Includes metalloids such as As. Recovery of the aryl ketone containing iodonium salt may be accomplished by standard methods using techniques such as filtration, centrifugation and the like.

The photopolymerizable composition of the present invention comprises a photopolymerizable organic substance and 0.1 to 15 based on the weight of the photopolymerizable organic substance.
It can be prepared by mixing with an effective amount of an aryl ketone-containing iodonium salt, which can be wt%. The aryl ketone-containing iodonium salt is 0.5% by weight to about 5% by weight.
It is preferred to use in an amount of The photopolymerizable composition of the present invention contains inactive ingredients such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fibers and processing aids in an amount of about 100 parts by weight of the filler per 100 parts by weight of the photopolymerizable organic substance. It can be contained in an amount of up to 500 parts by weight. The photopolymerizable composition can be applied to a substrate such as metal, rubber, plastic, film, molded member, paper, wood, glass, cloth, concrete and ceramic.

Examples of applications in which the photopolymerizable composition of the present invention can be used are protective, decorative and insulating coatings, pitting compounds, printing inks, sealants, adhesives, molding compounds, wire insulation materials. , Woven fabric coatings, laminates, impregnated tapes, varnishes, encapsulants for electronic components, etc. Examples of the present invention will now be given for better understanding of the present invention by those skilled in the art, but these are merely to illustrate the present invention and not to limit the present invention. In the examples, all parts are parts by weight. Example 1 A mixture of 0.025 mol of phenyliodo sotosylate and 0.05 mol of aryl ketone at 130-135 ° C.
The mixture was heated and stirred for an hour. During the reaction the mixture became homogeneous, then it was cooled and poured into 100 ml of ethyl ether.
An oil formed which was washed with diethyl ether and then dissolved in 50 ml methyl ethyl ketone. 5 g of potassium hexafluoroarsenate was added to the resulting solution. Immediately, a precipitate of potassium p-toluenesulfonate was formed, which was separated by filtration. The solvent was then removed on a rotary evaporator and the solid obtained was recrystallized from ethanol. Then, the UV absorption value (λ
_max ) was measured using a Beckman UV spectrophotometer.
The following results were obtained.

[0037]

[Chemical 21]

Example 2 A 1% solution of 3-benzoylphenylphenyliodonium hexafluoroarsenate in limonene dioxide was poured into an aluminum cup and irradiated from a GEH3T7 medium pressure mercury arc lamp for 5 minutes at 5 inches.
The solution was found to cure to a bottom of an aluminum cup at a thickness of 70.8 mils. Example 3 The same procedure as in Example 2 was repeated except that a 1% solution of diphenyliodonium hexafluoroarsenate in limonene dioxide was used. At the end of the 5 minute irradiation time, the solution was still incompletely cured at its surface and uncured below the surface. A 1% mixture of 3-benzoylphenylphenyliodonium hexafluoroarsenate and Shell Chemical Epon 812 (a mixture of bisphenol-A diglycidyl ether and butyl diglycidyl ether) was added as described in Example 2 at 2.5. Irradiated for minutes. The results were as follows.

[0039]

[Chemical formula 22]

The above results show that the UV curable composition of the present invention can be cured to a higher film thickness than prior art UV curable compositions using a diphenyliodonium salt as a photoinitiator. Example 4 A 1% solution of the photoinitiator in 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ERL4221) from Union Carbide Chemical Co. was placed in an aluminum cup according to the method of Example 3. Irradiated for 1 minute. The following results were obtained.

[0041]

[Chemical formula 23]

The above procedure was repeated except that a 1% solution of diphenyliodonium hexafluoroarsenate was used in place of the aromatic ketone-containing diphenyliodonium salt of the present invention. A cured film having a film thickness of about 14.3 mils was obtained. The above results further indicate that the UV curable compositions of the present invention exhibit superior deep cure properties as compared to prior art UV curable compositions.

Although the above examples show only a few of the very large number of variations that can be used in the practice of the present invention, the present invention is remarkably broader in deep UV.
It is to be understood that the curable cationically polymerizable compositions, the significantly broader range of arylketone-containing iodonium salts, and the broader range of methods of preparation of the materials as set forth in the detailed disclosure preceding these examples are directed. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 101/00 // C08F 2/50 MDN 7442-4J

Claims (6)

[Claims] 1. A following components: (A) a photopolymerizable organic material; and (B) ^{Formula: R 1 -I + -R X -} ( wherein, R C _(6-13) monovalent aromatic hydrocarbon Is a hydrogen group or a halo-substituted monovalent aromatic hydrocarbon group, R ¹ is a monovalent arylketone group which is bonded to iodine by a nuclear carbon atom to form a carbon-iodine bond, and X ⁻ is a counterion. )
An effective amount of an aryl ketone-containing iodonium photoinitiator;
A deep photopolymerizable organic resin composition containing: 2. The deep UV curable composition according to claim 1, wherein the cationically polymerizable organic substance is an epoxy resin. 3. An aryl ketone-containing iodonium salt is represented by: The deep UV curable composition according to claim 1, wherein 4. An iodonium salt containing an aryl ketone is represented by: The deep UV curable composition according to claim 1, wherein 5. An iodonium salt containing an aryl ketone is represented by: The deep UV curable composition according to claim 1, wherein 6. An aryl ketone-containing iodonium salt is represented by: The deep UV curable composition according to claim 1, wherein